EP1238962A1 - Procédé pour la préparation de produits d'addition de Michael - Google Patents
Procédé pour la préparation de produits d'addition de Michael Download PDFInfo
- Publication number
- EP1238962A1 EP1238962A1 EP02003307A EP02003307A EP1238962A1 EP 1238962 A1 EP1238962 A1 EP 1238962A1 EP 02003307 A EP02003307 A EP 02003307A EP 02003307 A EP02003307 A EP 02003307A EP 1238962 A1 EP1238962 A1 EP 1238962A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- alkyl
- possibly substituted
- process according
- linear
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 150000002576 ketones Chemical class 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- SHOJXDKTYKFBRD-UHFFFAOYSA-N 4-Methyl-3-penten-2-one, 9CI Chemical compound CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 5
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- ZAMCMCQRTZKGDX-SNAWJCMRSA-N (e)-3-methylpent-3-en-2-one Chemical compound C\C=C(/C)C(C)=O ZAMCMCQRTZKGDX-SNAWJCMRSA-N 0.000 claims description 3
- NXDRTDGIVDSDSG-UHFFFAOYSA-N 3-acetyl-4,4-dimethylheptane-2,6-dione Chemical compound CC(=O)CC(C)(C)C(C(C)=O)C(C)=O NXDRTDGIVDSDSG-UHFFFAOYSA-N 0.000 claims description 3
- ZAMCMCQRTZKGDX-UHFFFAOYSA-N 3-methylpent-3-en-2-one Natural products CC=C(C)C(C)=O ZAMCMCQRTZKGDX-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- VDOGJIOUXMQBSP-UHFFFAOYSA-N methyl 2-acetyl-3,3-dimethyl-5-oxohexanoate Chemical compound COC(=O)C(C(C)=O)C(C)(C)CC(C)=O VDOGJIOUXMQBSP-UHFFFAOYSA-N 0.000 claims description 3
- ICZWBUQSFIESGY-UHFFFAOYSA-N methyl 2-acetyl-3,4-dimethyl-5-oxohexanoate Chemical compound COC(=O)C(C(C)=O)C(C)C(C)C(C)=O ICZWBUQSFIESGY-UHFFFAOYSA-N 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical group C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005287 vanadyl group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 229910015900 BF3 Inorganic materials 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 6
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 229940093499 ethyl acetate Drugs 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 150000004820 halides Chemical group 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 2
- 238000007011 Robinson annulation reaction Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 description 1
- PZRYCGXPFKMYAB-UHFFFAOYSA-N 2-(4-fluoro-3-methylbenzoyl)-3,3-dimethyl-5-oxohexanoic acid Chemical compound CC(=O)CC(C)(C)C(C(O)=O)C(=O)C1=CC=C(F)C(C)=C1 PZRYCGXPFKMYAB-UHFFFAOYSA-N 0.000 description 1
- RCMSABHBOBOMFR-UHFFFAOYSA-N 3,4,5,6-tetrahydro-2h-pentalen-1-one Chemical compound C1CCC2=C1C(=O)CC2 RCMSABHBOBOMFR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/12—Ketones containing more than one keto group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/73—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
Definitions
- the present invention relates to the field of organic synthesis and more specifically to a process for the preparation of Michael-adducts, as defined below, by reacting a ⁇ , ⁇ - or a ⁇ , ⁇ -disubstituted, or a ⁇ , ⁇ , ⁇ -trisubstituted, ⁇ , ⁇ -unsaturated ketone (I) with a ⁇ -ketoester or a ⁇ -diketone (II) in presence of a suitable catalyst of formula M(X) n , according to scheme 1 :
- the present invention relates to a simple and general process, aimed at the synthesis of the compounds of formula (III) in a single step.
- groups which are possible substituents of R 1 , R 2 , R 3 , R 4 , R', R" and of the ring, which two of said R 1 to R 4 may form together are C 1 -C 7 alkyl, alkenyl or alkoxy groups, C 5 -C 7 cycloalkyl or cycloalkenyl groups, or aromatic rings possibly substituted by a C 1 -C 8 alkyl or alkoxy group or a halide atom.
- Q represents a R' or a OR' group ;
- groups which are possible substituents of R 1 , R 2 , R 3 , R 4 , R', R" and of the ring, which two of said R 1 to R 4 may form together are C 1 -C 4 alkyl, alkenyl or alkoxy groups, C 5 -C 6 cycloalkyl or cycloalkenyl groups or aromatic groups possibly substituted by a C 1 -C 6 linear or branched alkyl or alkoxy group or a halide atom.
- the compound of formula (I) is 4-methyl-3-penten-2-one or 3-methyl-3-penten-2-one, and the compound of formula (II) is 2,4-pentanedione or a C 1 -C 4 alkyl ester of the 3-oxo-butanoate.
- Preferred catalysts of formula M(X) n are those wherein M is selected from the group consisting of the 3d transition metals, the lanthanides, the trimethylsilane group (Me 3 Si), the vanadyl group (VO 3+ ), the alkaline metals, Sc, Y, Sn, Pb, Al and Bi ;
- Groups which are possible substituents of Z and R are, for example, halides atomts, C 1 to C 6 alkyl or alkoxy groups or non-coordinatng nitrogen containing groups.
- M is selected from the group consisting of Cu, Zn, Y and Yb ;
- the catalyst may be added to the reaction media as a pure and isolated chemical or it can be prepared in situ , by several methods, in the reaction medium, without isolation or purification, just before its use.
- One of the possible procedures to advantageously prepare in situ a catalyst according to the invention consists in reacting an appropriate anhydrous metal salt of formula M(acac) n or M(RCOO) n , R being defined as herein above and n being an integer from 2 to 3, with n equivalents, in respect to the metal, of BF 3 ⁇ OEt 2 in a solvent, e.g. an ester.
- a solvent e.g. an ester
- the catalyst can be added to the reaction medium in a large range of concentration.
- concentration values ranging from 0.001 to 0.1 molar equivalents, relative to the ⁇ , ⁇ -unsaturated ketone (I).
- the catalyst concentration will be comprised between 0.005 and 0.05 molar equivalents. It goes without saying that the optimum concentration of catalyst will depend on the nature of the latter and on the desired time of reaction.
- the process of the invention can be carried out in presence or absence of solvent, but in any case it is advantageously performed in anhydrous conditions, wherein by anhydrous is intended a content in water below 1% by weight, preferably below 0.5%.
- a solvent is required, it is possible to use a pure solvent or a mixture of solvents.
- Said solvent is chemically compatible with the reaction and does not deactivate the catalyst, e.g. a weakly or non-coordinating solvent.
- Preferred solvents for the process of the invention are selected from the group consisting of ethers, carboxylic acids, esters, ketones, aromatic solvent, linear or branched or cyclic hydrocarbons, chlorinated solvents and mixture thereof. More preferably, the solvent is selected from the group consisting of C 4 -C 6 ethers, C 2 -C 8 esters, C 3 -C 6 ketones, acetic acid, methylene chloride and mixture thereof.
- the temperature at which the process of the invention can be carried out is comprised between -20°C and 100°C, preferably between 0°C and 50°C.
- a person skilled in the art is also able to select the preferred temperature as a function of the melting and boiling point of the starting and final products and/or an eventual solvent.
- the process of the invention may also be advantageously carried out under pressure of an inert gas such as nitrogen.
- an inert gas such as nitrogen.
- a pressure ranging from 1.5 bar to 20 Kbar, preferably from 2 to 200 bar, may be used.
- a suspension of 0.135 g of Cu(acac) 2 (0.517 mmole) is stirred at 25°C in 0.7 g of ethylacetate.
- Boron trifluoride etherate (0.154 g ; 1.08 mmole) is added over 30 min. at 30°C and agitation is continued for 2 h.
- the resulting homogeneous solution is added as such to a mixture of 6 g of methyl 3-oxo-butanoate (51.7 mmole) and 5.07 g of 4-methyl-3-penten-2-one (51.7 mmole).
- the resulting solution is stirred at room temperature over 16 h and finally heated at 60°C for an hour.
- the solvent and the unreacted material (starting materials) are distilled out under reduced pressure.
- the oily residue is distilled, in a bulb to bulb apparatus, at 110-130°C under 1-2 mbar. 4 g of methyl 2-acetyl-3,3-dimethyl-5-oxo-hexanoate are obtained (>95% purity) corresponding to 36% yield.
- a suspension of 0.135 g of Cu(acac) 2 (0.517mmole) is stirred at 25°C in 0.7 g of ethylacetate.
- Boron trifluoride etherate (0.154 g ; 1.08 mmole) is added over 30 min. at 30°C and agitation is continued for 2 h.
- the resulting homogeneous solution is added as such to a mixture of 6 g of 2,4-pentanedione (60 mmole) and 5.88 g of 4-methyl-3-penten-2-one (60 mmole).
- the resulting solution is stirred at room temperature over 6 h and finally heated at 50°C for an hour.
- a suspension of 0.135 g of Cu(acac) 2 (0.517 mmole) is stirred at 25°C in 0.7 g of ethylacetate.
- Boron trifluoride etherate (0.154 g ; 1.08 mmole) is added over 30 min, at 30°C and agitation is continued for 2 h.
- the resulting homogeneous solution is added as such to a mixture of 6 g of methyl 3-oxo-butanoate (51.7 mmole) and 5.07 g of 3-methyl-3-penten-2-one (51.7 mmole).
- the resulting solution is stirred at room temperature.
- the solvent and the unreacted material are distilled out under reduced pressure.
- the oily residue is distilled, in a bulb to bulb apparatus, at 110-130°C under 1-2 mbar. 6.5 g of methyl 2-acetyl-3,4-dimethyl-5-oxo-hexanoate (mixture of 4 diastereoisomers) are obtained, corresponding to 58.5% yield.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| WOPCT/IB01/00318 | 2001-03-07 | ||
| IBPCT/IB01/00318 | 2001-03-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1238962A1 true EP1238962A1 (fr) | 2002-09-11 |
| EP1238962B1 EP1238962B1 (fr) | 2008-02-27 |
Family
ID=11004049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02003307A Expired - Lifetime EP1238962B1 (fr) | 2001-03-07 | 2002-02-13 | Procédé pour la préparation de produits d'addition de Michael |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6686498B2 (fr) |
| EP (1) | EP1238962B1 (fr) |
| JP (1) | JP4138337B2 (fr) |
| AT (1) | ATE387421T1 (fr) |
| DE (1) | DE60225199T2 (fr) |
| ES (1) | ES2299538T3 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104159884A (zh) * | 2012-02-03 | 2014-11-19 | 株式会社Lg生命科学 | 通过使用水或多种酸作为添加剂的新型麦克尔加成反应制备化合物的方法 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2806008B1 (fr) * | 2000-03-08 | 2002-09-27 | Centre Nat Rech Scient | Catalyseur solide de structure hydrotalcite integrant des ions fluorures |
| US7279605B2 (en) * | 2004-11-11 | 2007-10-09 | Firmenich Sa | Synthesis of cyclopentenones |
| WO2011111460A1 (fr) * | 2010-03-11 | 2011-09-15 | 独立行政法人科学技術振興機構 | Catalyseur à base de bore supporté sur un polymère et procédé de production d'un produit de la réaction d'addition de michaël utilisant ce catalyseur |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0088423A2 (fr) * | 1982-03-08 | 1983-09-14 | Daikin Kogyo Co., Ltd. | Fluorocétones ainsi que leurs produits cycliques de condensation |
| EP0826652A1 (fr) * | 1995-03-22 | 1998-03-04 | Nagase & Company, Ltd. | Procede pour l'elaboration d'un compose asymetrique a l'aide d'un complexe metallique |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5017649A (en) * | 1988-01-19 | 1991-05-21 | Eastman Kodak Company | Low temperature Michael addition reactions |
-
2002
- 2002-02-13 EP EP02003307A patent/EP1238962B1/fr not_active Expired - Lifetime
- 2002-02-13 AT AT02003307T patent/ATE387421T1/de not_active IP Right Cessation
- 2002-02-13 DE DE60225199T patent/DE60225199T2/de not_active Expired - Lifetime
- 2002-02-13 ES ES02003307T patent/ES2299538T3/es not_active Expired - Lifetime
- 2002-02-14 US US10/077,551 patent/US6686498B2/en not_active Expired - Lifetime
- 2002-03-07 JP JP2002061871A patent/JP4138337B2/ja not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0088423A2 (fr) * | 1982-03-08 | 1983-09-14 | Daikin Kogyo Co., Ltd. | Fluorocétones ainsi que leurs produits cycliques de condensation |
| EP0826652A1 (fr) * | 1995-03-22 | 1998-03-04 | Nagase & Company, Ltd. | Procede pour l'elaboration d'un compose asymetrique a l'aide d'un complexe metallique |
Non-Patent Citations (6)
| Title |
|---|
| DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; SORIENTE, ANNUNZIATA ET AL: "K10 montmorillonite catalysis", XP002195727, retrieved from STN Database accession no. 131:257027 * |
| DATABASE CROSSFIRE BEILSTEIN [online] Beilstein Institut zur Förderung der Chemischen Wissenschaften, Frankfurt am Main, DE; XP002195726, Database accession no. 3743097 * |
| GREEN CHEM. (1999), 1(3), 157-162 * |
| KOTSUKI H ET AL: "Yb(OTf)3-CATALYZED MICHAEL ADDITION REACTIONS OF beta-KETOESTERS ON SILICA GEL SUPPORTS AND AT HIGH PRESSURE", TETRAHEDRON LETTERS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 38, no. 43, 27 October 1997 (1997-10-27), pages 7583 - 7586, XP004189848, ISSN: 0040-4039 * |
| SORIENTE A ET AL: "Solvent Free Reaction Under Microwave Irradiation: A New Procedure For Eu-Catalyzed Michael Addition of 1,3-Dicarbonyl Compounds", TETRAHEDRON LETTERS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 38, no. 2, 13 January 1997 (1997-01-13), pages 289 - 290, XP004070527, ISSN: 0040-4039 * |
| WILLIAM G. DAUBEN: "Organic reactions at high pressure. Michael addition of activated acyclic donors with beta,beta-disubstituted enone acceptors.", TETRAHEDRON LETTERS, vol. 24, no. 36, 1983, pages 3841 - 3844, XP001062825 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104159884A (zh) * | 2012-02-03 | 2014-11-19 | 株式会社Lg生命科学 | 通过使用水或多种酸作为添加剂的新型麦克尔加成反应制备化合物的方法 |
| CN104159884B (zh) * | 2012-02-03 | 2016-01-13 | 株式会社Lg生命科学 | 通过使用水或多种酸作为添加剂的新型麦克尔加成反应制备化合物的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1238962B1 (fr) | 2008-02-27 |
| DE60225199D1 (de) | 2008-04-10 |
| DE60225199T2 (de) | 2009-03-05 |
| JP2002308818A (ja) | 2002-10-23 |
| ES2299538T3 (es) | 2008-06-01 |
| US6686498B2 (en) | 2004-02-03 |
| US20020128504A1 (en) | 2002-09-12 |
| JP4138337B2 (ja) | 2008-08-27 |
| ATE387421T1 (de) | 2008-03-15 |
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